Processes of color photography and compositions and elements therefor for utilizing sulfonamide color formers



?atented Feb. 10, 1948 COMPOSITIONS AND ELEMEN'IIS TIgIEBE- FOR FOR UTILIZING SULFONAMIDECOL- OR FORMERS Andrew B. Jennings, New Brunswick, N.-'--J., as-

jsignor to E. I. du Pont de Nemours&ompany, ""Wilmington, Del., a corporation of Delaware No-Drawing. 0rigin'al application Aprilf16i1943, Serial' No. 483,333,=now Pjattent NoI-2j395j484, dated February 26-, 1946. bivided and thiS ap plication May 10, 1945, SerialNo. 593,090

- 4 Claims. (01595- 6) 1 This invention relates to color photography. More'parti'cularmit' relates to processes of color photography Wherein'dyeimages are produced during the development of silver salt images and to photographic elements and compositions therefor. Still- 'moreparticularly, it relates to processesof color photography wherein naphtholsulfonamides of aromatic polyamines which have a reactiveposition -qrtho 0r para tothe hydroxyl group are utilized as color coupling components, dye intermediates, or color formers.

A large numberof varied components or dye intermediates that couple with the development product of an aromatic primary amino color coupling developing agents during the development of "reducible Y silver salt have been. proposed for photographic processes. *They are .aptly named color-formers and have such a structure or contain such components or. groups that they form under conditions of" development quinoneimine or azomethine-dyes. Immobile or non-diffusing and substantive-color formers of the above type which consist of phenol, naphthol, aniline, naphthylamine, aminonaphthol nuclei, and nuclei'of compounds having a reactive methylene group, e. g., acylacetic acidand cyanoacetic acid, esters, and amides, pyrazolones, hydrindenes, and coumaranones but which are of suflicient molecular weight or contain such groups that they are substantive to gelatin or non-diffusing therein have also beenproposed for such processes. In fact, sulfonamides of various types have been suggested, including-developer and emulsion component types. Manyofsuch coloriormers have been found to be commercially unsatisfactory because the dye images formed by their use decompose by the action of heat andlight. Many have a deleterious effect on light-sensitive silver halide grains and desensitize the same. Somereduce the gamma of light-sensitive silver halide layers below the utility level. Others, including sulfonamides of 1,5-a-niino'naphthols, desensitize andare-not-of-the-proper shade for a blue-green orminus-red color former.

-An object' ofthisinvention is to provide new and useful' -photogra-phiccolor processes. Afurther object is to provide photographic elements which contain a new-class of naphthol derivativ'es'which are stable to heatand moisture when incorporated therein. A still further object isto provide photographic elementswithsuch derivatives which are free from deleterious :action on light-sensitive-silver halidefgrains. A further object-is to provide suchfs color formers which form 'heat- :andlight-stable dye images upon colon-coupling development of reducible images. A more specific obj ect is to provide photographic elements with-a dye intermediate which forms ablue-green dye of the proper spectral characteristics for 3--'color. -photography. Other -objects areto (provide: a neww-process of color. photography-randcompositions therefor and to contribute a general advance to the art. Still other objects will bezapparent tothose. familiar with color photography from the .tollowing description.

It has been. found- :that naphtholxzsulfonamides of the! general aformula:

wherein a position ortho cream-tome hydroxyl groups'is reactive and Ais the divalent radical of an organic diamine of at leasteight carbon atomsand having" at least one benzene nucleus maybepr'epared in" a practical manner; and' are well suitedior dye" intermediates or color "formers in processes "of color photography utilizing color coupling procedures in the 'form'ati'on of idyestufi images.

The radical A obviously'may 'vary' somewhat andwith the imino groups fconstitute the residue of Various aromatic 'dia'mines such as 1,5-idiamino naphthalene, 2,'2'- .2,4-."- and 4,4-'diaminostilbenes p'ara diamin'odiphenylether, benzidine, 1,4'-bis ('beta'aniinbnithyb' benzene, 1,4-bis (betaa'minoeth'yll benzene, and the like. The hydrocarbon nuclei of such residues may contain variousinnocuousra di'cals or, grou'ps'which do not enter into dye "coupling reactions with diazo compounds'or developer "components, such "as hydrocarbon ra'dicals; ethergroups, halogen groups, hitro groupsf'etc. v

"Positions"o'rtho or para tothe hydroxyl groups may be unsubstituted ormay contain a reactive group," e. g., a chlorine or P bromine atom --or"-a s'ulfonic orcarboxylio acid group.

The dinaphtholsulfonanii'des or 'aroriiatic diamines described above seem to possess novel, unique, and evensurprising'properties when they are incorporated into a 'waterpermeable colloid layer. such 'as aigelatin:layer 'of a color yielding photographic "element. T-hese propertiesare evidenced especially in a multilayer photographic pletely removed from a gelatin dispersion containing the compound by washing the same in neutral, aqueous media, yet when the compound is utilized in the blue-green layer of a multilayer film no loss of color separation is obtained when the film is processed in a. conventional manner.

Naphtholsulfonyl chlorides which have a reactive position ortho or para to the alpha hydroxyl groups can be utilized for the preparation of the disulfonamides of di-amines of Formula 1. The disulfonamides, in general, are prepared by a simple condensation of the naphtholsulfonyl chlorides and diamines in the substantial absence of water, e. g., under anhydrous conditions, or alternatively in aqueous media. A basic agent such as Pyridine, trialkylamines, triethanolamine, sodium carbonate, sodium hydroxide, sodium acetate, may be present, if desired. Inert organic solvents, e. g., ether, acetone, acetic acid, dioxane, may be used as reaction media, if desired. However, when the basic agent is also a solvent such agents need not be used.

The naphthol sulfonyl chlorides may be prepared from naphthol sulfonic acids such as the 1,2- and 1,5-isomers. Prior to the preparation of the sulfonyl chlorides, however, the phenolic hydroxyl group should be protected. This may be accomplished by treatment with chloroformic ester or by acylation, e. g., with acetic anhydride, acetyl chloride, etc. The procedure in Monatsh., vol. 53-54, page 105 (1929), may advantageously be used. The sulfonic acid groups can be converted to sulfonyl chloride groups with phosphorous pentachloride after the hydroxyl groups have been taken care of. The preparation of representative disulfonamides will be outlined further below.

In making color yielding elements in accordance with this invention, the dinaphtholsulfonamides of aromatic diamines may be brought into solution or fine dispersion with a solvent such as ethyl alcohol or by means of a hydrotropic agent and water and then mixed with an aqueous dispersion of a water-permeable or reversible colloid, e. g., gelatin, agar agar, gum arabic, albumin, synthetic gelatin, and other binding agents used in layers for photographic elements and coated on a film base or support having a substratum suitable for anchoring silver halide layers thereto. The gelatin dispersions may be coated directly onto a light-sensitive silver halide layer or stratum or onto a water-permeable layer coated on such layer or stratum. In the case of coloryielding elements for contact or imbibition development of the type described in U. '8. Patents 2,328,034 and 2,369,171, the dispersions may be coated directly onto a base or support (1) free from reducible silver salt layers, or (2) in a noncoactive relationship with a reducible silver salt layer of such element, e, g., a subbed film base. The dye intermediates also may be admixed with gelatin silver halide emulsions and coated to form single or multi-layer photographic elements. Other dye intermediates which form dyes of the proper spectral characteristics for 3-color photography may be used in the other color yielding layers of the elements.

The invention will be further illustrated but is not intended to be limited by the following examples: Example 1 A solution of 2 grams of 1,4-diaminodiphenylether and 6.5 parts of l-carbethoxynaphthol-2- sulfonyl chloride having the formula (iJOOOCaH:

were admixed in 250 cos. of dry ether and refluxed for a period of about 2 hours. Two cos. of pyridine were added and refluxing was continued for about A.; hour more. Water was then added to theether solution and the ether was steam distilled off. The viscous semi-solid formed was dried and digested with absolute alcohol. On

standing the product crystallized and was washed on on [ID-SOaNHO-OONH-SO By using one molar equivalent of the l-carbethoxynaphthol-Z-sulfonyl chloride per molar equivalent of diamine and reacting these components in the same manner, the following resuits were obtained with the amines listed below:

Amine Nature of bisulionamide p-Xylylenediamine .Viscous oil. 1,5-Naphthylenediamine Solid.

p,p-Diaminodiphenylmethane.

Do. 4,4'-Diaminodiphenylmethane-3,3'- Solid M. P. 245-248" C.

dicarboxylic acid.

p-Bis-(a-aminoethyl) benzene Solid.

Example I] kaline solution of the following composition: N-diethyl-p-phenylene diamine hydrochloride grams 2 Sodium sulfite (anhydrous), do 5 Sodium carbonate (anhydrous) -do 20 Water to cc 1,000

whereby a dye image is formed in situ with a metallic silver image. The silver and silver salts are then removed by means of Farmers reducer and a blue-green dye image of good spectral qualities remains. The image is a very stable indophenol dye. A 48 hour exposure to the carbon arc of a Fadometer" produces no perceptible change. ineither shade, or intensity.

Moreover; i3 weeks""-storage at 1209: and 95 931' relative humidity" producesa barely-perceptible change.

-When' the specific bis-naphthosu'lfonamide dyes in the list following-Example I-are incor porated in a light-sensitive silver halide'element; 1. exposed and processed in like manner; strong blue-green dye images of good spectral qualities: which are stable toheat; moisture; andlightare I v 'wz:

While the above "examples are limited to ethe 4 production of a single color element}; the invenformed in each'instance;

tion is" obviously notiimited to' that aspectz On the-contrary; the novel bis-naphtholsulfonamides +15 structures, including multilayer elements -forcan be used in photographic elements ofvarious" multl color photography; e.:g.', monopa'cks or bipacks. novel-color yielding elements and'processes of photography'utilizing the compounds.

Example III A photographic silver halide emulsion: containing 4Af-bis-(l-naphthol 2 sulfonamidophenyl) ether prepared after the manner statedv inExample II is coated onto atransparent col-- lulosea'cetate filmbasev A. layer of colloidal silver in gelatin is deposited ontothe opposite side ofthe film base. On-the latter is coated awphotographic silverv halideemulsion containing diacetoamino-12,4,5-benZo -bisthiaZole' as an orange-red.color former; The element can then be used: for the production;'of two colorzprints.

in the following manner:

The side containing the color former of' EX- ample I is exposed to anegativerecord of the rediaspects of a colored object, andzthe sidecon-w taining. the orange-red color "former is exposed to a negative record of the'greenaspects of...the.

same colored object.v The element isthen developed for 15 minutes ina bath of the following:

composition:

N-diethyl-p-phenylene diamine hydrochloride rams 3 Sodium carbonate. (anhydrous) do 30 Sodium sulfite (anhydrous) do 1 Potassium bromide -.s do .25

Water to cc; 1,000-

whereby dye images are formed simultaneously in the two light-sensitive layers. and treatment with Farmersreducer, acolored representation of the. originalobject remains Example I V An element for. 3-color.prints or transparencies can be made by. depositingzomazcellulose acetate film base-a positive type non-color-sensitize'd silver halide emulsion, whichzcontains asa yellow color former N-furoylacet-N -benzoylacetbenzidine. The preparation of this compound is givenin U. S. Patent 2,319,426; On the opposite- The following examples are directed to After washing ram-lone):isi'exposed with:blue lightatosa negatives: record -or the gi eentaspectsfloila'scolored' subject and on the same: side; oiith'e' supporti is l printed with red. light theredzcomponent-negative record-1 of 'tiie subject The light'sensitive layer onther:

opposite side of the' support-'is exposed with blues light to the blue-component ne'gativerecord of theasubject: The element: is processed;bythecproer cedure of Example III, whereupon-iai colorei re production-of theoorig-inalisubject is obtained;:

Example V element somewhatasimilar, :to' "that of' Ex=.- ampleIV canzbe maderbyzplacingxhe color form ersizin a: separate r-gelatin layerLrather' than in that respective silver. halid emulsion layers. Such a;. filmzelem'ent: may;.-compriseiniorder 'a film base, ar-gelatin layer-containing the di-(l-naphthol-2 sulfonamideo Off. 1;4-:'-'diaminodi'phenyl ether," 9;: red sensitive silver?- halide gelatin "layer, a gelatimz layer: containing; 4;4i=-bis'- lz-naphthol-2 sulfonav amidophenyl) eth'er; .a;:- gelatin layer containing: 4A" methyleneiwbis- (m 'stearoylaminophenyl methyl pyrazolone); asfia color: former, a. green H sensitive silver halide igelatin layer; a gelatin lay'ler containing. 'tartitazinw as a yellow filter dye;- a gelatihplayercontaining Ni-furoylacet-N -ben zoylacetbenzidine; and: finally a blue-sensitive: gelatin silver:halide:layer.' This may ,be exposedto an originalrcolorxscener and processed as foblows: "-1:

The exposed element -is developed for- 15 min utes in the following baths Hydroquinone grams 8? Metol do 22 Sodium carbonate (anhydrous) do 60 Sodium sulfite (anhydrous): -do 40 Potassium bromide do 3 .5.- Potassium thiocyanate do 2L0-v Water to cc 1,000

After washing ior' 10 minutes; the-element" is exposed to whitelighband then developed for=25 minutes in the fol-lowing 'bathi N-diethyl-p-phenylenediamine hydroch1o-- ride lgram's 3'? Sodium :carbonate: (anhydrousi -clo; 30; Water to cc 1,000

Following. washing. and .removal of. silver with Earmers reducen-a positive color reproductionl of the original scene is obtained;

The novel bis-naphthol-sulf.onamides of aromatic diamines may contain inthe benzene:

nuclei any of" the common substituents which give desirable properties to dyes. Such. substituents include hydroxyl, amino (--NH2 hy. drocarbon substituted amino, halogen, alkoxyl, hydrocarbon; e. g.j,. alky1,'ary1, and.aralkyl;.carboxyl; nitrile, sulionic, sulione, sulfinic, sulfide,. nitro', etc.

The bis-naphthol' sulfonamides of aromatic diiamines maybe'dispersed in gelatin or equivalent water-permeable reversible colloid binding agents, e. g., albumin, agar agar, polyglucuronic acid, etc.; or they may be admixed with resins or cellulose derivatives and dispersed in such colloid layers containing light-sensitive materials or coated on light-sensitive silver salt layers.

The color yielding elements may contain light-sensitive layers composed of simple or mixed silver halides which may contain the usual sensitizers, desensitizers, stabilizers, fog inhibitors, emulsion hardeners, etc. Suitable types include silver chloride, silver bromide, silver chlorabromide, silver chloride-bromide-iodide, silver bromide-iodide, etc, which may contain cyanine,

photography. They may be used with other color I coupling developing agents than those specifically described in the examples. The diamino aryl compounds such as para-phenylene-diamine and its substitution products are preferred. These developers may be substituted in the amino groups as well as in the ring, preferably the former, to constitute compounds such as the monoand di-alkyl arylenediamines, including the monoand di-alkyl naphthylenediamines, alkyl phenylenediamines and alkyl toluylenediamines. The compounds, of course, must have one free primary or unsubstituted amino group which enables the oxidation product of the developer to couple with the color forming cornpounds. As examples of developers of the class described, there may be mentioned p-amino-diethylaniline, 1,4-naphthylenediamine, 4-diethylamino-l-naphthylamine. The salts'of the bases which may be organic or inorganic are, in general, more soluble and more stable than the free bases. The hydrochlorides and sulfates have great utility in preparing the developing solutions. Hydrazines as set forth in U. S. Patent 2,209,929 may also be used according to the process of U. S. Patent 2,339,213.

The bi-naphtholsulfonamides of Formula 1 are believed to be new compounds. Their use in photographic processes, as stated above, leads to superior, unique, and unexpected results. The spectral quality of quinoneimine dyes produced by color coupling development of two representative dyes shown in the spectro photometric curves of the drawing evidence their superior properties. Fig. 1 is that of a minus red Wratten filter. Fig. 2 is that of the quinoneimine dye from N-diethyl-p-phenylene diamine hydrochloride and the bi-(Naphthol-1,2sulfonamide) of 1,4-bis-(betaaminoethyl) benzene and Fig. 3 is that of the quinoneimine dye from N-diethyl-pphenylenediamine hydrochloride and the color former of Example I.

The compounds seem unique in that they may be used in multilayer films without loss of color separation but they can be Washed from a gelatin dispersion by washing in neutral aqueous media. This indicates they are not substantive or non-difiusing in the ordinary sense.

The blue-green or minus red characteristics of the dyes formed upon color development of images with the color formers of this invention shown in the curves evidences that they are well suited for processes of multi-color photography.

In addition to their outstanding spectral qualities of the dye images produced in color develop: ment procedures, the compounds have excellent stability to heat and light. A further advantage resides in the fact that the color formers do not desensitize silver halide emulsions and reduce gamma below the utility level. The color forzners, moreover, seem to increase the relative sensitivity of emulsions exposed to White and blue light, whereas previously proposed sulfonamides of aminonaphthols desensitize such emulsions.

This application is a, division of application Serial Number 483,333, filed April 16, 1943, now Patent Number 2,395,484, issued February 26, 1946.

As many apparently Widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined in the appended claims.

I claim:

1. A process of color photography which comprises developing a reducible silver salt image with a color coupling developing agent in the presence of a 4,4'-bis-(1naphthol-2-sulfonamidophenyl) ether.

2. A process of color photography which comprises developing a reducible silver salt image with an aromatic primary amino color develop ing agent in the presence of 4,4-bis-(1-naphthol-2-sulfonamidophenyl)ether and removing the silver and silver salts.

3. A photographic element comprising a support having at least one light-sensitive silver halide layer and at least one water-permeable stratum containing 4,4'-bis-(1-naphtho1-2-sulfonamidophenyl) ether.

4. A photographic element comprising a, support bearing a light-sensitive silver halide colloid layer containing a 4,4-bis(1-naphthol-2-sulfonamidophenyl) ether.

ANDREW B. JENNINGS.

REFERENCES CITED The following references are of record in the file of this patent:

503,752 Great Britain Apr. 11, 1939 Certificate of Correction Patent No. 2,435,629. February 10, 1948.

ANDREW B. JENNINGS It is hereby certified that error appears in. the printed specification of the above numbered patent requ' ing correction as follows: Column 4, line 47, in the table, first column thereof, for p-Bis-(a-aminoethyl) benzene read p-B'Ls-(B-am'inoethyl) benzene; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

5 Signed and sealed this 25th day of May, A. D. 1948.

THOMAS E MURPHY,

Assistant Commissioner of Patents. 

